DE3621265A1 - N-SULFENYLATED 2-TRIFLUORMETHYL BENZIMIDAZOLES - Google Patents

Description

The invention relates to new N-sulfenylated 2-trifluoromethyl benzimidazole, a process for their preparation and their use as herbicides and microbicides.

It is already known that certain N-sulfenylates Indazole have fungicidal and microbicidal properties (see US-P-38 67 540). The effect of these compounds is however in certain indication areas, under certain conditions, such as B. at low Application quantities and concentrations, not always satisfactory.

New N-sulfenylated 2-trifluoromethyl found benzimidazoles of the general formula (I),

in which
X and Y independently of one another represent halogen,
n stands for 0, 1, 2 or 3 and
R ¹ and R ^{2 are the} same or different and stand for hydrogen, halogen, each optionally substituted by halogen substituted alkyl, alkoxy or alkylthio or together represent a fused ring optionally substituted by halogen and optionally interrupted by heteroatoms.

It was also found that the new N-sulfenylated 2-trifluoromethyl-benzimidazoles of the formula (I),

in which
X and Y independently of one another represent halogen,
n stands for 0, 1, 2 or 3 and
R ¹ and R ^{2 are the} same or different and represent hydrogen, halogen, each optionally substituted by halogen substituted alkyl, alkoxy or alkylthio or together represent a fused ring optionally substituted by halogen and optionally interrupted by heteroatoms,
obtained when 2-trifluoromethyl-benzimidazoles of the formula (II)

in which
R ¹ and R ^{2 are the} same or different and have the meaning given above,
with sulfenoic acid halides of formula (III)

ZS-CX _n Y _{3- n} (III)

in which
X, Y and n have the meaning given above and
Z represents halogen, preferably chlorine or bromine,
in the presence of a diluent and in the presence of an acid binder.

Finally it was found that the new N-sulfenylated 2-Trifluoromethyl-benzimidazoles of the formula (I) strong exhibit herbicidal and microbicidal properties.

The active substances according to the invention surprisingly show of formula (I) a higher herbicidal and antimicrobial Efficacy than that known from the prior art Compounds of the same type of action.

In the context of the definition of substituents, halogen stands for Fluorine, chlorine, bromine and iodine, preferably for fluorine, chlorine and Bromine, particularly preferred for fluorine and chlorine.

Alkyl preferably represents a carbon chain with 1 to 6, particularly preferably 1 to 4 and very particularly preferably with 1 or 2 carbon atoms, such as Methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl sec-butyl, tert-butyl and pentyl.

Alkoxy preferably represents alkoxy with a carbon chain from 1 to 4, particularly preferably 1 to 3 and very particularly preferably from 1 or 2 carbon atoms, such as methoxy, ethoxy, n- and i-propoxy.

Alkylthio is preferably alkylthio with a carbon chain with 1 to 4, particularly preferably from 1 to 3 carbon atoms and very particularly preferably from 1 Carbon atom.  

R ¹ and R ² together also represent a fused-on, preferably 5- or 6-membered ring which is interrupted by oxygen, sulfur and / or nitrogen, preferably by 1 or 2 oxygen and / or sulfur atoms and which is one or more times can be substituted by halogen, preferably fluorine, chlorine and bromine, in particular by fluorine and chlorine. R ¹ and R ² are in particular the radicals -O-CHF-CF ₂ O-, -O-CF ₂ -CFCl-O- and -O-CF ₂ -CF ₂ -O-. n generally represents 0, 1, 2 or 3, preferably 1, 2 or 3, particularly preferably 2 or 3 and in particular 2.

N-Sulfenylated 2-trifluoromethylbenzimidazoles of the formula (I) are preferred, in which
X and Y independently of one another represent fluorine, chlorine and bromine,
n represents 0, 1, 2 or 3, and
R ¹ and R ^{2 are the} same or different and are hydrogen, fluorine, chlorine, bromine, each optionally one or more times substituted by fluorine, chlorine and / or bromine alkyl having 1 to 6 carbon atoms, alkoxy and alkylthio each having 1 to 4 carbon atoms stand or R ¹ and R ² together represent a 5- or 6-membered, fused ring which can be interrupted by oxygen, nitrogen and / or sulfur and can be substituted one or more times by fluorine, chlorine and / or bromine.

Those compounds of the formula (I) in which
X and Y independently of one another represent fluorine, chlorine and bromine,
n stands for 2 or 3 and
R ¹ and R ^{2 are the} same or different and are hydrogen, fluorine, chlorine, bromine, in each case optionally one to five times substituted by fluorine, chlorine and / or bromine alkyl having 1 to 4 carbon atoms, alkoxy or alkylthio each having 1 to 3 carbon atoms stand or R ¹ and R ² together represent a 5- or 6-membered, fused ring which can be interrupted by 1 or 2 oxygen and / or sulfur atoms and can be substituted one to four times by fluorine, chlorine and / or bromine.

Those N-sulfenylated 2-trifluoromethyl-benzimidazoles of the formula (I) in which are very particularly preferred
X and Y independently of one another represent fluorine or chlorine,
n stands for 2 or 3 and
R ¹ and R ^{2 are the} same or different and are hydrogen, fluorine, chlorine, bromine, methyl, fluoromethyl, difluoromethyl, trifluoromethyl, chloromethyl, dichloromethyl, trichloromethyl, chlorodifluoromethyl, difluoromethyl, methoxy, fluoromethoxy, dichloromethoxy, trifluoromethoxy, chlorodifluoromethoxy, dichlorofluoromethoxy, dichlorofluoromethoxy, dichlorofluoromethoxy, dichlorofluoromethoxy, dichlorofluoromethoxy, dichloromifluoromethoxy, dichloromifluoromethoxy, dichloromifluoromethoxy, dichloromifluoromethoxy, dichloromifluoromethoxy, dichloromifluoromethoxy, dichloromifluoromethyl, dichloromethyl , 1,2,2-tetrafluoroethoxy, 2-chloro-1,1,2-trifluoroethoxy, 2,2,2-trifluoroethoxy, 2,2-dichloro-1,1,2-trifluoroethoxy, 2-chloro-1,1 , 2,2-tetrafluoroethoxy, 2-chloro-2,2-difluoroethoxy, 2,2-dichloro-2-fluoroethoxy, 2,2,2-trichloroethoxy, 1,1,2,3,3,3-hexafluoropropoxy, methylthio , Chlorodifluoromethylthio, difluoromethylthio, trifluoromethylthio, 5,6-dioxomethylene, 5,6-dioxodifluoromethylene, 5,6-dioxo-chlorofluoromethylene, 5,6-dioxoethylene, 5,6-dioxodifluoroethylene, 5,6-dioxotrifluoroethylene, 5,6 -Dioxotetrafluoroethylene, 5,6-dioxo-chlorotrifluoroethylene, 5,6-dioxo-dichlorodifluoroethylene, 5,6-dioxo-chlorodifluoroethylene, 5,6-dioxochlorofluoroethylene or 5,6-dioxo-dichlorofluoroethylene.

The following N-sulfenylated 2-trifluoromethylbenzimidazoles of the formula (I) may be mentioned by way of example. Positional isomers are also conceivable with regard to the sulfenyl radical:
1-dichlorofluoromethylsulfenyl-4-trifluoromethoxy-2-trifluoromethyl-benzimidazole,
1-dichlorofluoromethylsulfenyl-5-trifluoromethoxy-2-trifluoromethyl-benzimidazole,
1-dichlorofluoromethylsulfenyl-6-trifluoromethoxy-2-trifluoromethyl-benzimidazole,
1-dichlorofluoromethylsulfenyl-7-trifluoromethoxy-2-trifluoromethyl-benzimidazole,
1-dichlorofluoromethylsulfenyl-4-trifluoromethyl-7-chloro-2-trifluoromethyl-benzimidazole,
1-dichlorofluoromethylsulfenyl-5-difluoromethoxy-2-trifluoromethyl-benzimidazole,
1-dichlorofluoromethylsulfenyl- [2-chloro-1,1,2-trifluoroethoxy] - 2-trifluoromethyl-benzimidazole,
1-dichlorofluoromethylsulfenyl-5-chloride-difluoromethoxy-2-trifluoromethyl-benzimidazole,
1-dichlorofluoromethylsulfenyl-4-chloro-5-trifluoromethoxy-2-trifluoromethyl-benzimidazole,
1-dichlorofluoromethylsulfenyl-4-methyl-5-trifluoromethoxy-2-trifluoromethyl-benzimidazole,
1-dichlorofluoromethylsulfenyl-5-bromo-6-fluoro-2-trifluoromethyl-benzimidazole,
1-dichlorofluoromethylsulfenyl-5,7-dimethyl-6-trifluoromethyl-2-trifluoromethyl-benzimidazole,
1-dichlorofluoromethylsulfenyl-4-trifluoromethylthio-2-trifluoromethylbenzimidazole,
1-dichlorofluoromethylsulfenyl-5-trifluoromethylthio-2-trifluoromethylbenzimidazole,
1-dichlorofluoromethylsulfenyl-6-trifluoromethylthio-2-trifluoromethylbenzimidazole,
1-dichlorofluoromethylsulfenyl-7-trifluoromethylthio-2-trifluoromethyl-benzimidazole,
1-dichlorofluoromethylsulfenyl-5-dichlorofluoromethylthio-2-trifluoromethyl-benzimidazole,
1-dichlorofluoromethylsulfenyl-5-difluoromethoxy-2-trifluoromethyl-benzimidazole,
1-dichlorofluoromethylsulfenyl-5-trifluoromethyl-2-trifluoromethyl-benzimidazole
1-dichlorofluoromethylsulfenyl-4- [2,2,2-trifluoroethoxy] -2-trifluoromethyl-benzimidazole,
1-dichlorofluoromethylsulfenyl-5- [2,2,2-trifluoroethoxy] -2-trifluoromethyl-benzimidazole,
1-dichlorofluoromethylsulfenyl-4- [1,1,2,2-tetrafluoroethoxy] -2-trifluoromethyl-benzimidazole,
1-dichlorofluoromethylsulfenyl-5- [1,1,2,2-tetrafluoroethoxy] -2-trifluoromethyl-benzimidazole,
1-dichlorofluoromethylsulfenyl-5,6- [dioxotetrafluoroethylene] - 2-trifluoromethyl-benzimidazole
1-dichlorofluoromethylsulfenyl-5,6- [dioxo-chlorotrifluoroethylene] - 2-trifluoromethyl-benzimidazole,
1-dichlorofluoromethylsulfenyl-6- [2-chloro-1,1,2-trifluoroethoxy] - 5-methyl-2-trifluoromethyl-benzimidazole,
1-dichlorofluoromethylsulfonyl-5- [2-chloro-1,1,2-trifluoroethoxy] - 6-methyl-2-trifluoromethyl-benzimidazole,
1-dichlorofluoromethylsulfenyl-5,6-bis-trifluoromethoxy-2-trifluoromethyl-benzimidazole.

For example, if 5-trifluoromethoxy-2-trifluoromethyl benzimidazole and dichlorofluoromethanesulfonic acid chloride as starting materials, the course of the reaction can the method of the invention by the following Formula scheme can be reproduced.

The to carry out the inventive method as Starting materials required 2-trifluoromethyl-benzimidazoles are generally defined by formula (II).

R ¹ and R ² preferably have the meaning that has already been mentioned for these symbols in connection with the description of the substances of the formula (I) according to the invention.

The 2-trifluoromethyl-benzimidazoles of the formula (II) are partially known (see e.g. DE-OS 16 42 334), partially are they the subject of a parallel German Patent application.

The compounds of formula (II) are in principle known processes (see, for example, M. A. Phillips, J. Chem. Soc. 1928, 2393-2399 and W. T. Smith, E. C. Steinle. J. Am. Chem. Soc. 75, 1292-1294 (1952)).

They can be obtained, for example, from o-phenylenediamines of the formula (IV)

in which
R ¹ and R ^{2 have} the meaning given above,
with reflux with trifluoroacetic acid in the presence of 4N hydrochloric acid and optionally in the presence of a diluent, such as water, or if the hydrochlorides of the o-phenylenediamines of the formula (IV) are reacted in an analogous manner.

Some of the starting materials of the formula (IV) are known (see e.g. EP-A-1 27 763). The not yet known o-phenylenediamines Formula (IV) are partially the subject a unpublished patent application DE-P 36 05 977 from February 25, 1986 and partially one in parallel German patent application filed.

The new and also the known compounds of the general Formula (IV) can be prepared (see e.g. L. M. Yagupolskÿ, et. al., Zh. obsh. Khim 33, 3051-5 (1963); Houben-Weyl, volume X / 1, p. 559 (1971) and volume XI / 1, pp. 472-3 (1957) and manufacturing examples by for example compounds of formula (V)

in the
R ¹ and R ^{2 have} the meaning given above,
first acylated on the amino group, then in the 2-position to the acylated amino group with a nitrating agent such as nitrating acid, optionally in the presence of a diluent such as glacial acetic acid, and optionally in the presence of a catalyst such as acetic anhydride at temperatures between -20 and + 50 ° C introduces a nitro group, hydrogenates the nitro group in the presence of a catalyst, such as Raney nickel, and in the presence of a diluent, such as methanol, at hydrogen pressures of 10 to 100 bar and at temperatures between +20 and + 80 ° C to the amino group and then the acyl group is split off again in the customary manner, for example by saponification with aqueous or alcoholic base.

The compounds of formula (V) are known and leave are produced in an analogous manner by known processes (see e.g. EP 11 179).

The sulfenoic acid halides of the formula (III) required as starting materials for carrying out the process according to the invention are generally known compounds of organic chemistry. In this formula, X, Y and n preferably have the meaning which have already been mentioned for these radicals in the description of the substances of the formula (I) according to the invention, Z preferably represents chlorine or bromine.

As a solvent and / or diluent come for Process according to the invention in particular: aromatic Hydrocarbons such as benzene or toluene; halogenated Hydrocarbons such as methylene chloride or Carbon tetrachloride; Nitriles such as acetonitrile or Propionitrile; Ethers such as tetrahydrofuran or dioxane; as well as esters such as ethyl acetate.

As acid binders for the process according to the invention all common organic and inorganic acid binders be used. These preferably include tertiary Amines such as triethylamine or pyridine; Alkali hydroxides and / or alkali carbonates such as sodium and potassium hydroxide, as well as sodium hydrogen carbonate and potassium carbonate.

The reaction temperatures can when carrying out the Process according to the invention in a larger area can be varied. Generally one works at temperatures between 0 and 150 ° C, preferably between 20 and 100 ° C.  

To carry out the method according to the invention the indazoles of the formula (II) and the sulfenoic acid halides of formula (III) in general in equimolar amounts a. It is preferred to use trifluoromethylbenzimidazole per mole of the formula (II) about 0.8 to 3, particularly preferred 0.85 to 1.5 moles of sulfenic acid halide of the formula (III) a.

Isolation of the new N-sulfenylated 2-trifluoromethylbenzimidazoles the general formula (I) takes place in common way, for example Add water to the reaction mixture, extraction with an organic solvent, chromatography or Distillation.

In the benzimidazoles of the formula (I), which differ from symmetrical Derive diamines of formula (II), it is through suitable reaction management possible, different on Nitrogen sulfenylated products or mixtures thereof receive.  

The active compounds according to the invention can be used as defoliants, Desiccants, herbicides and especially as Weed killers are used. Under weeds in the broadest sense, all plants are to be understood that growing up in places where they are undesirable. If she Substances according to the invention as total or selective herbicides work depends essentially on the applied Amount off.

The active compounds according to the invention can, for. B. in the following Plants are used:

Dicotyledon weeds of the genera: Sinapis, Lepidium, Galium, Stellaria, Matricaria, Anthemis, Galinsoga, Chenopodium, Urtica, Senecio, Amaranthus, Portulaca, Xanthium, Convolvulus, ipomoea, polygonum, sesbania, ambrosia, cirsium, Carduus, Sonchus, Solanum, Rorippa, Rotala, Lindernia, Lamium, Veronica, Abutilon, Emex, Datura, Viola, Galeopsis, Papaver, Centaurea.

Dicotyledon cultures of the genera: Gossypium, Glycine, Beta, Daucus, Phaseolus, Pisum, Solanum, Linum, Ipomoea, Vicia, Nicotiana, Lycopersicon, Arachis, Brassica, Lactura, Cucumis, Cucurbita.

Monocotyledon weeds of the genera: Echinochloa, Setaria, Panicum, Digitaria, Phleum, Poa, Festuca, Eleusine, Brachiaria, Lolium, Bromus, Avena, Cyperus, Sorghum, Agropyron, Cynodon, Monochoria, Fimbristylis, Sagittaria, Eleocharis, Scirpus, Paspalum, Ischaemum, Sphenoclea, Dactyloctenium, Agrostis, Alopecurus, Apera.  

Monocot cultures of the genera: Oryza, Zea, Triticum, Hordeum, Avena, Secale, Sorghum, Panicum, Saccharum, Pineapple, Asparagus, Allium.

However, the use of the active compounds according to the invention is by no means limited to these genres, but extends in the same way for other plants.

The compounds are suitable depending on the concentration for total weed control z. B. on industrial and track systems and on paths and squares with and without Tree growth. Likewise, weed control compounds in permanent crops, e.g. B. forest, ornamental wood, Fruit, wine, citrus, nut, banana, coffee, tea, Gum, oil palm, cocoa, berry fruit and hop plants and for selective weed control in annuals Cultures are used.

The active compounds according to the invention are suitable for combating of mono- and dicotyledon weeds, in the fore and Post-emergence in mono- and dicotyledonous cultures, such as for example cotton, corn and wheat.  

The active ingredients can be in the usual formulations are transferred, such as solutions, emulsions, wettable powders, Suspensions, powders, dusts, pastes, soluble Powders, granules, suspension emulsion concentrates, Active substance-impregnated nature and synthetic substances as well as very fine encapsulation in polymeric substances.

These formulations are prepared in a known manner e.g. B. by mixing the active ingredients with extenders, So liquid solvents and / or solid Carriers, optionally using surfactants Agents, i.e. emulsifiers and / or Dispersing agents and / or foaming agents.

In the case of the use of water as an extender e.g. B. also organic solvents as auxiliary solvents be used. As a liquid solvent essentially come into question: aromatics, such as xylene, Toluene, or alkylnaphthalenes, chlorinated aromatics and chlorinated aliphatic hydrocarbons, such as chlorobenzenes, Chlorethylene or methylene chloride, aliphatic Hydrocarbons, such as cyclohexane or paraffins, e.g. B. petroleum fractions, mineral and vegetable oils, Alcohols, such as butanol or glycol, and their ethers and Esters, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar solvents, such as dimethylformamide and dimethyl sulfoxide, and water.

The following are suitable as solid carriers:

For example, ammonium salts and natural rock powder, such as Kaolins, clays, talc, chalk, quartz, attapulgite,  Montmorillonite or diatomaceous earth and synthetic rock powder, such as finely divided silica, aluminum oxide and silicates, come as solid carriers for granules in question: e.g. B. broken and fractionated natural rocks such as calcite, marble, pumice, sepiolite, dolomite as well synthetic granules from inorganic and organic Flours and granules from organic material such as sawdust, Coconut shells, corn cobs and tobacco stems; as Emulsifying and / or foaming agents are possible: e.g. B. non-ionic and anionic emulsifiers, such as polyoxyethylene Fatty acid esters, polyoxyethylene fatty alcohol Ethers, e.g. B. alkylaryl polyglycol ethers, alkyl sulfonates, Alkyl sulfates, aryl sulfonates and protein hydrolyzates; as dispersants come into question: z. B. Lignin sulfite liquor and methyl cellulose.

In the formulations, adhesives such as carboxymethyl cellulose, natural and synthetic powdery, granular or latex-shaped polymers can be used, such as Gum arabic, polyvinyl alcohol, polyvinyl acetate, as well natural phospholipids such as cephalins and lecithins and synthetic phospholipids. Other additives can be mineral and vegetable oils.

Dyes such as inorganic pigments, e.g. B. Iron oxide, titanium oxide, ferrocyan blue and organic dyes, such as alizarin, azo and metal phthalocyanine dyes and trace nutrients such as salts of iron, manganese, Boron, copper, cobalt, molybdenum and zinc can be used.  

When used as a herbicide, the formulations contain or fungicide generally between 0.1 and 95 Weight percent active ingredient, preferably between 0.5 and 90%.

The active compounds according to the invention can be used as such or in their formulations also in a mixture with known ones Find herbicides for weed control, wherein Ready formulations or tank mixes are possible.

Known herbicides such as z. B. 1-amino-6-ethylthio-3- (2,2-dimethylpropyl) -1,3,5-triazine 2,4 (1H, 3H) -dione or N- (2-benzothiazolyl) -N, N'-dimethyl- urea for weed control in cereals; 4- Amino-3-methyl-6-phenyl-1,2,4-triazin-5 (4H) -one for weed control in sugar beet and 4-amino-6- (1,1-dimethylethyl) - 3-methylthio-1,2,4-triazin-5 (4H) -one for Weed control in soybeans, in question.

Mixtures with chloroacetic acid-N- (methoxymethyl) -2,6-diethylanilide, 2-ethyl-6-methyl-N- (1-methyl-2-methoxyethyl) - chloroacetanilide, N-methyl-2- (1,3- benzothiazol-2-yloxy) acetanilide, N, N-diisopropyl-S- (2,3,3-trichlorallyl) thiolcarbamate, N, N-di-n-propyl-thiocarbamic acid S-ethyl ester, exo-1-methyl -4- (1-methylethyl) -2- (methylphenylmethoxy) - 7-oxabicyclo- [2.2.1] -heptane, 1-methyl-3-phenyl-5- [3-trifluoromethylphenyl] -4 (1H) - pyridinone, methyl 2- [4,5-dihydro-4-methyl-4- (1-methylethyl) -5-oxo-1H-imidazol-2-yl] -4 (5) methylbenzoate, 2- [1- (Ethoxamino) butylidene] -5- (2-ethylthiopropyl) -1,3-cyclohexanedione, 3-isopropyl-2,1,3-benzothiadiazin-4-one-2,2-dioxide, 6-chloro-3-phenyl -pyridazin-4-yl-5-octyl-thiocarbonate, N-benzothiazolyl-N-methyl-N'-methylurea, N, N-dimethyl-N '- (3-chloro-4-methylphenylurea, 2-chloro N - {[4-methoxy-6-methyl-1,3,5-triazin-2-yl) amino] carbonyl} benzenesulfonamide, N, N-dimethyl-N ′ - (4-isopropylphenyl) urea, N, N-Dimethyl-N ′ - (3-trifluoromethyl-phenyl) urea, 4-E thylamino-2-t-butylamino-6-methylthio-s-triazine, 2-chloro-4,6-bis (ethylamino) -1,3,5-triazine, 2-chloro-4-ethylamino-6-isopropylamino-1 , 3,5-triazine, 2-chloro-4-ethylamino-6- (3-cyanopropylamino) -1,3,5-triazine, 4-amino-6-tert-butyl-3-methylthio-4,5- dihydro-1,2,4-triazin-5-one, 2- [4 β5-dichloropyrid-2-yloxy) phenoxy] propionic acid trimethylsilylmethyl ester, 2- {4 - [(3-chloro-5-trifluoromethyl-2 -pyridyl) -oxy] -phenoxy} - propanoic acid, 2- [4- (2,4-dichlorophenoxy) -phenoxy] - methyl propionate, 2,4-dichlorophenoxyacetic acid, 2,4-dichlorophenoxy propionic acid, (2-methyl-4 -chlorophenoxy) acetic acid, (4-chloro-2-methylphenoxy) propionic acid, methyl 5- (2,4-dichlorophenoxy) -2-nitrobenzoate, 3,5-diiodo-4-hydroxybenzodinitrile, 3, 5-dibromo-4-hydroxybenzonitrile, N- (1-ethoxypropyl) -3,4-dimethyl-2,6-dinitroaniline,
come into question. Surprisingly, some mixtures also have a synergistic effect.

Also a mixture with other known active ingredients, such as Fungicides, insecticides, acaricides, nematicides, protective substances against bird feed, plant nutrients and soil structure improvers is possible.

The active ingredients as such, in the form of their formulations or the one prepared therefrom by further dilution Application forms, such as ready-to-use solutions, Suspensions, emulsions, powders, pastes and granules are used will. They are used in the usual way e.g. B. by pouring, spraying, spraying, scattering. It is also possible to use the active ingredients according to the ultra-low-volume Apply the process or the preparation of the active ingredient or inject the active ingredient into the soil yourself. It can also the seeds of the plants are treated.  

The active compounds according to the invention can be used both before and can also be applied after the plants have emerged.

They can also be worked into the soil before sowing will.

The amount of active ingredient used can be used when Herbicide fluctuate in a wider range. It hangs essentially depends on the type of effect desired. In general, the application rates are between 0.01 and 10 kg of active ingredient per hectare of soil, preferably between 0.05 and 5 kg per ha.

The N-sulfenylated 2-trifluoromethyl-benzimidazoles of Formula (I), especially the N-dichlorofluoromethylthio-2- trifluoromethyl-benzimidazoles, also have a strong Microbicidal action and can help fight unwanted Microorganisms are used. The active ingredients are for use as crop protection agents, especially as fungicides, suitable or in material protection can be used to protect technical materials.

Fungicides in crop protection are used for Control of Plasmodiophoromycetes, Oomycetes, Chytridiomycetes, Zygomycetes, Ascomycetes, Basidiomycetes, Deuteromycetes.

Bactericidal agents are used in plant protection to combat from Pseudomonadaceae, Rhizobiaceae, Enterobacteriaceae, Corynebacteriaceae and Streptomycetaceae used.  

Some pathogens of fungal and bacterial diseases that fall under the generic names listed above may be mentioned as examples, but not by way of limitation:
Xanthomonas species, such as, for example, Xanthomonas campestris pv. Oryzae;
Pseudomonas species, such as, for example, Pseudomonas syringae pv. Lachrymans;
Erwinia species, such as, for example, Erwinia amylovora;
Pythium species, such as, for example, Pythium ultimum;
Phytophthora species, such as, for example, Phytophthora infestans;
Pseudoperonospora species, such as, for example, Pseudoperonospora humuli or Pseudoperonospora cubense;
Plasmopara species, such as, for example, Plasmopara viticola;
Peronospora species, such as, for example, Peronospora pisi or P. brassicae;
Erysiphe species, such as, for example, Erysiphe graminis;
Sphaerotheca species, such as, for example, Sphaerotheca fuliginea;
Podosphaera species, such as, for example, Podosphaera leucotricha;
Venturia species, such as, for example, Venturia inaequalis;
Pyrenophora species, such as, for example, Pyrenophora teres or P. graminea
(Conidial form: Drechslera, Syn: Helminthosporium);
Cochliobolus species, such as, for example, Cochliobolus sativus (conidial form: Drechslera, Syn: Helminthosporium);
Uromyces species, such as, for example, Uromyces appendiculatus;
Puccinia species, such as, for example, Puccinia recondita;
Tilletia species, such as, for example, Tilletia caries;
Ustilago species, such as, for example, Ustilago nuda or Ustilago avenae;
Pellicularia species, such as, for example, Pellicularia sasakii;
Pyricularia species, such as, for example, Pyricularia oryzae;
Fusarium species, such as, for example, Fusarium culmorum;
Botrytis species, such as, for example, Botrytis cinerea;
Septoria species, such as, for example, Septoria nodorum;
Leptosphaeria species, such as, for example, Leptosphaeria nodorum;
Cercospora species, such as, for example, Cercospora canescens;
Alternaria species, such as, for example, Alternaria brassicae;
Pseudocercosporella species, such as, for example, Pseudocercosporella herpotrichoides.

The good plant tolerance of the active ingredients in the Control of plant diseases necessary concentrations allows treatment of parts of plants above ground, of seed and seed, and of the soil.

When treating parts of plants, the drug concentrations can when used as a fungicide in the Application forms can be varied in a larger area. They are generally between 1 and 0.0001% by weight. %, preferably between 0.5 and 0.001%.

When treating seeds, amounts of active ingredient are generally used from 0.001 to 50 g per kilogram of seed. preferably 0.01 to 10 g.  

When treating the soil are active ingredient concentrations from 0.00001 to 0.1% by weight, preferably from 0.0001 to 0.02%, required at the site of action.

In addition, the active compounds of the invention Formula (I) has good effectiveness in combating Soil insects, nematodes and hygiene pests.

According to the invention, technical materials are not living Materials prepared for use in engineering have been. For example, technical Materials created by active ingredients according to the invention microbial change or destruction are protected should, adhesives, glue, paper and cardboard, textiles, Leather, wood, paints and plastic articles, cooling lubricants and other materials from microorganisms can be attacked or decomposed. As part of the materials to be protected are also parts of Production sites, for example cooling water circuits, called that impaired by the multiplication of microorganisms can be. Within the scope of the present invention are preferred as technical materials Adhesives, glues, papers and cartons, leather, wood, paints, Called cooling lubricants and cooling circuits.

As microorganisms that breakdown or change which can cause technical materials for example bacteria, fungi, yeasts, algae and slime organisms called. The agents according to the invention preferably act  Active substances against fungi, in particular molds, wood-discoloring and wood-destroying fungi (Basidiomycetes), as well as against bacteria, mucus organisms and Seaweed.

Microorganisms of the following genera may be mentioned, for example:
Alternaria, such as Alternaria tenuis,
Aspergillus, such as Aspergillus niger,
Chaetomium, like Chaetomium globosum,
Coniophora, such as Coniophora puteana,
Lentinus, such as Lentinus tigrinus,
Penicillium, such as Penicillium glaucum,
Polyporus, such as Polyporus versicolor,
Aureobasidium, such as Aureobasidium pullulans,
Sclerophoma, such as Sclerophoma pityophila,
Trichoderma, like Trichoderma viride,
Escherichia, such as Escherichia coli,
Pseudomonas, such as Pseudomonas aeriginosa,
Staphylococcus, such as Staphylococcus aureus.

Depending on the field of application, an active ingredient according to the invention are converted into the usual formulations, such as solutions, emulsions, suspensions, powders, pastes and granules.  

These can be produced in a manner known per se, e.g. B. by mixing the active ingredients with an extender, that of liquid solvent and / or solid Carriers exist, optionally using of surface-active agents, such as emulsifiers and / or Dispersants, if necessary in the case of use of water as an extender organic solvents how alcohols can be used as aids.

Liquid solvents for the active ingredients can, for example Water, alcohols, such as lower aliphatic Alcohols, preferably ethanol or isopropanol, or Benzyl alcohol, ketones, such as acetone or methyl ethyl ketone, liquid hydrocarbons, such as gasoline fractions, halogenated Hydrocarbons such as 1,2-dichloroethane.

Microbicidal agents contain when used for protection technical materials, the active ingredients in general an amount of 1 to 95%, preferably 10 to 75%.

The application concentrations of the active compounds according to the invention depend on the type and occurrence of the combating microorganisms, as well as according to the composition of the material to be protected. The optimal amount to use can be determined by test series. In general the application concentrations are in the range from 0.001 to 5% by weight, preferably from 0.05 to 1.0 % By weight, based on the material to be protected.  

The active compounds according to the invention can also be mixed with other known active ingredients. For example the following active substances may be mentioned: benzyl alcohol mono (poly) hemiformal and other formaldehyde releasing Compounds, benzimidazolyl methyl carbamates, tetramethylthiuram disulfide, Zinc salts of dialkyldithiocarbamates, 2,4,5,6-tetrachloroisophthalonitrile, thiazolylbenzimidazole, Mercaptobenzthiazole, 2-rhodanidomethylthiobenzthiazole, Organotin compounds, methylene bisthiocyanate, Phenol derivatives, such as 2-phenylphenol, (2,2'- Dihydroxy-5,5′-dichloro) diphenylmethane and 3-methyl-4- chlorophenol.

The preparation and use of the active compounds according to the invention can be seen from the examples below:

Manufacturing examples example 1 1-dichlorofluoromethylsulfenyl-2,5-bis (trifluoromethyl) benzimidazole

To 25.4 g (0.1 mol) of 2,6-bis (trifluoromethyl) benzimidazole and 10.1 g (0.1 mol) of triethylamine in 120 ml of dichloromethane are between 20 ° C and 30 ° C within about one 16.9 g (0.1 mol) of dichlorofluoromethylsulfenyl chloride, dissolved in 120 ml of dichloromethane, were added dropwise. The mixture is stirred at the same temperature for 2 h, the precipitated triethylamine hydrochloride is filtered off with suction and washed with dichloromethane. The filtrate combined with the washing phase is washed twice with water. After drying (MgSO ₄ ), the volatile constituents are distilled off in a water jet vacuum. The oily residue is filtered chromatographically over a short silica gel (eluent: toluene).
Yield: 32.4 g (83.8% of theory).
Boiling point: 103-105 ° C / 0.2 mbar

In the table below they are analogous prepared compounds of formula (I) listed. The Compounds were recrystallized for purification, distilled or by chromatography on silica gel Dichloromethane or toluene as the eluent.  

Table 1

Examples of use Example A Pre-emergence test

Solvent: 5 parts by weight of acetone Emulsifier: 1 part by weight of alkylaryl polyglycol ether

For the preparation of a suitable active ingredient preparation is mixed 1 part by weight of active ingredient with the specified Amount of solvent, gives the specified amount of emulsifier and dilute the concentrate with water on the desired concentration.

Seeds of the test plants are sown in normal soil and watered with the preparation of active compound after 24 hours. The amount of water per unit area is expediently kept constant. The concentration of active substance in the preparation is irrelevant, the only decisive factor is the amount of active substance applied per unit area. After three weeks, the degree of damage to the plants is rated in% damage compared to the development of the untreated control. It means:
0% = no effect (like untreated control)
100% = total annihilation

In this test, e.g. B. the compounds according to the preparation examples 1 and 2 in addition to a very good herbicidal Efficacy against dicotyledon weeds, such as  Chenopodium, Datura, Matricaria, purslane and Stellaria and monocot weeds, such as Cyodon has a very good crop tolerance, in particular in cotton and wheat.  

Example B Post emergence test

Solvent: 5 parts by weight of acetone Emulsifier: 1 part by weight of alkylaryl polyglycol ether

For the preparation of a suitable active ingredient preparation you mix 1 part by weight of active ingredient with the specified amount of solvent, gives the specified Amount of emulsifier and dilute the concentrate with Water to the desired concentration.

Test plants which have a height of 5-15 cm are sprayed with the active compound preparation in such a way that the desired amounts of active compound are applied per unit area. The concentration of the spray liquor is chosen so that the particular amounts of active compound desired are applied in 2000 l of water / ha. After three weeks, the degree of damage to the plants is rated in% damage compared to the development of the untreated control.
It means:
0% = no effect (like untreated control)
100% = total annihilation

In this test, e.g. B. the compounds according to the preparation examples 1, 2 and 3 in addition to a very good herbicidal Effect against dicot weeds, such as  Chenopodium, Sinapis, Solanum and against monocot Weeds, such as Echinochloa and Poa, too very good crop tolerance, in particular in corn and cotton.  

Example C Pyricularia test (rice) / protective

Solvent: 12.5 parts by weight of acetone Emulsifier: 0.3 part by weight of alkylaryl polyglycol ether

For the preparation of a suitable active ingredient preparation is mixed 1 part by weight of active ingredient with the specified Amount of solvent and dilute the concentrate with water and the specified amount of emulsifier to the desired Concentration.

To test for protective effectiveness, young people are sprayed Rice plants with the active ingredient preparation to dripping wet. After the spray coating has dried, the Plants with an aqueous spore suspension of Pyricularia oryzae inoculated. Then the Plant in a greenhouse at 100% rel. humidity and set up at 25 ° C.

The evaluation of the Disease.

A clear superiority in effectiveness over the prior art show in this test z. B. the connections according to production examples 2 and 6.  

Example D

To demonstrate the effectiveness against fungi, the minimum Inhibitory concentrations (MIC) of the invention Active ingredients determines:

An agar made from wort and peptone is mixed with active substances according to the invention in concentrations of 0.1 mg / l to 5000 mg / l. After the agar solidifies, it is contaminated with pure cultures of the test organisms listed in the table. After 2 weeks of storage at 28 ° C and 60 to 70% rel. Humidity is determined the MIC. MIC is the lowest concentration of active ingredient at which no growth occurs due to the type of microbe used. Show good effects e.g. B. the compounds according to Preparation Examples 1, 2, 3, 5, 6, 7 and 8 on the test organisms:
Alternaria tenuis, Asperigillus niger, Aureobasidium pullulans, Chaetomium globosum, Cladosporium cladosporioides, Lentinus tigrinus Penicillium glaucum, Sclerophoma pityophila, Trichoderma viride.

Example E Action against bacteria

An agar containing broth as the nutrient medium is also used Active substances according to the invention in concentrations of 1 to 5000 ppm added. The medium is then infected each with the test organisms listed in Table II and keep the infected medium at 28 ° C and 60 for 2 weeks up to 70% rel. Humidity. The MIC is the lowest Concentration of active ingredient with no growth by the type of microbe used. The MIC values are shown in Table II.

Table E

Specification of the MIC values in mg / l when the active substances specified below act on bacteria.

Claims (9)

1. N-sulfenylated 2-trifluoromethylbenzimidazoles of the general formula (I) in which
X and Y independently of one another represent halogen,
n stands for 0, 1, 2 or 3 and
R ¹ and R ^{2 are the} same or different and stand for hydrogen, halogen, each optionally substituted by halogen substituted alkyl, alkoxy or alkylthio or together represent a fused ring optionally substituted by halogen and optionally interrupted by heteroatoms. 2. N-sulfenylated 2-trifluoromethylbenzimidazoles of the formula (I) according to claim 1, in which
X and Y independently of one another represent fluorine, chlorine and bromine,
n stands for 0, 1, 2 or 3 and
R ¹ and R ^{2 are the} same or different and are hydrogen, fluorine, chlorine, bromine, in each case optionally substituted one or more times by fluorine, chlorine and / or bromine alkyl having 1 to 6 carbon atoms, alkoxy and alkylthio each having 1 to 4 carbon atoms stand or R ¹ and R ² together represent a 5- or 6-membered, fused ring which can be interrupted by oxygen, nitrogen and / or sulfur and can be substituted one or more times by fluorine, chlorine and / or bromine. 3. N-sulfenylated 2-trifluoromethyl-benzimidazoles of the formula (I) according to claim 1, in which
X and Y independently of one another represent fluorine, chlorine and bromine,
n stands for 2 or 3 and
R ¹ and R ^{2 are the} same or different and are hydrogen, fluorine, chlorine, bromine, in each case optionally one to five times substituted by fluorine, chlorine and / or bromine alkyl having 1 to 4 carbon atoms, alkoxy or alkylthio each having 1 to 3 carbon atoms stand or R ¹ and R ² together represent a 5- or 6-membered, fused ring which can be interrupted by 1 or 2 oxygen and / or sulfur atoms and can be substituted one to four times by fluorine, chlorine and / or bromine. 4. Process for the preparation of N-sulfenylated 2-trifluoromethylbenzimidazoles of the formula (I), in which
X and Y independently of one another represent halogen,
n stands for 0, 1, 2 or 3 and
R ¹ and R ^{2 are the} same or different and stand for hydrogen, halogen, each optionally substituted by halogen substituted alkyl, alkoxy or alkylthio or together represent a fused-on ring optionally substituted by halogen and optionally interrupted by heteroatoms,
characterized in that 2-trifluoromethylbenzimidazoles of the formula (II) in which
R ¹ and R ^{2 are the} same or different and have the meaning given above,
with sulfenic acid halides of the formula (III) ZS-CX _n Y _{3- n} , 6 (III) in which
X, Y and n have the meaning given above and
Z represents halogen, preferably chlorine or bromine,
in the presence of a diluent and in the presence of an acid binder. 5. Herbicidal and microbicidal agents, characterized by containing at least one N-sulfenylated 2-trifluoromethyl-benzimidazole of the formula (I) according to claims 1 to 4. 6. Process for combating weeds, characterized in that that N-sulfenylated 2-trifluoromethyl  benzimidazoles of the formula (I) according to the claims 1 to 4 on the weeds and / or their Living space. 7. Process for combating microbes, thereby characterized in that N-sulfenylated 2-trifluoromethyl benzimidazoles of the formula (I) according to the claims 1 to 4 on microbes and / or their habitat can act. 8. Use of N-sulfenylated 2-trifluoromethyl-benzimidazoles of formula (I) according to claims 1 to 4 to control weeds. 9. Process for the preparation of herbicidal and microbicidal Means, characterized in that N- Sulfenylated 2-trifluoromethyl-benzimidazoles Formula (I) according to claims 1 to 4 with extenders and / or surface-active substances mixed.